Supplement to Model-aided Design and Integration of Functionalized Hybrid Nanomaterials for EnhancedBioremediation of PFASs Using Supercritical Fluid Chromatography/Mass Spectrometry

使用超临界流体色谱/质谱法增强 PFAS 生物修复功能化混合纳米材料的模型辅助设计和集成的补充

• 批准号: 10601888
• 负责人: Diana S Aga
• 金额: $ 2.75万
• 依托单位: STATE UNIVERSITY OF NEW YORK AT BUFFALO
• 依托单位国家: 美国
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-08-04 至 2024-10-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/10601888
• 关键词: Acids; Aftercare; Amino Acids; Anaerobic Bacteria; Binding; Biodegradation; Biological; Bioremediations; Blood; Carbon; Chemicals; Communities; Degradation Pathway; Development; Docking; Environment; Environmental Pollution; Enzymes; Evolution; Excision; Exposure to; Fluorine; Genes; Genetic Transcription; Goals; Hazardous Chemicals; Health; Human; Hybrids; Hydrogen Peroxide; Industrialization; Iron; Kidney; Kinetics; Knowledge; Link; Malignant Neoplasms; Malignant neoplasm of liver; Mass Spectrum Analysis; Measurable; Measures; Metagenomics; Metals; Microbiology; Minerals; Modeling; Molecular; NMR Spectroscopy; Nanotechnology; Non-Insulin-Dependent Diabetes Mellitus; Outcome; Oxidation-Reduction; Oxides; Pathway interactions; Persons; Poison; Poly-fluoroalkyl substances; Production; Property; Public Health; Research; Resolution; Risk; Site; Source; Structure; Supercritical Fluid Chromatography; System; Techniques; Technology; Testing; Toxic effect; Toxicokinetics; Training; Work; catalyst; consumer product; dehalogenation; design; drinking water; efficacy testing; exposed human population; graphene; ground water; improved; in silico; innovation; liver injury; microbial; microbial community; microbial genome; mineralization; molecular dynamics; molecular modeling; nano; nanomaterials; novel; prevent; rRNA Genes; remediation; substance use; titanium dioxide; tool; transcriptomics; ultraviolet irradiation

ABSTRACT Global public health concern is growing over per- and polyfluoroalkyl substances (PFASs) toxicity, environmental persistence, and potential to bioaccumulate in humans and wildlife. Nearly every person who has been tested for PFASs shows measurable levels in their blood resulting from contamination of the environment and continued use in consumer products and industrial applications. In particular, drinking water appears to be the major source of PFAS exposure for people living near contaminated sites. Importantly, some PFASs have been linked to liver damage, developmental impacts, and several cancers (e.g., kidney, testicular). Environmental remediation is urgently needed, but efforts are hampered by the extreme persistence of the carbon-fluorine bond. Biodegradation typically involves only the non-fluorinated components of polyfluorinated PFASs, resulting in the creation of shorter-chain perfluorinated acids that are more persistent and mobile. Complete mineralization has not been demonstrated. Abiotic treatment technologies can be more effective but require extremely high energy inputs, and the degradation mechanisms are poorly understood. There is a critical need for a treatment technology with lower energy requirements, and for enhanced degradation pathways that efficiently mineralize PFASs without formation of perfluorinated acids that persist after treatment. The overarching goal of this proposal is to develop an innovative nanomaterial-biological strategy to tackle the challenge of PFAS biodegradation. Our central hypothesis is that pretreatment by tailored nanomaterials can facilitate transformation of structurally diverse PFASs to achieve more efficient and complete biodegradation. Our previous work has shown that functionalized nanohybrid catalysts incorporating reduced graphene oxide (rGO) and nano zerovalent iron (nZVI) can successfully initiate degradation of long-chain PFASs. Here, we will employ this abiotic transformation as an innovative pretreatment to unlock the biodegradation of PFASs. Leveraging our expertise in molecular modeling and ‘omics’ techniques, we will test and tailor the ability of microbial communities to more efficiently degrade pretreated PFASs and their initial degradation products. All degradation products will be characterized by high-resolution mass spectrometry and 19F-nuclear magnetic resonance spectroscopy to reveal the mechanisms that enable this nano-bioremediation strategy. This research will tackle a pressing environmental contamination problem with three complementary specific aims: Aim 1: Synthesize multifunctional redox-active nanohybrid materials and evaluate their catalytic properties for PFAS degradation (dehalogenation, degradation of long-chains to short-chains). We will synthesize and characterize two multifunctional and hierarchical carbon-metal nanohybrids: (i) redox-active reduced graphene oxide nano zerovalent iron (rGO–nZVI) and (ii) photocatalytic rGO-nZVI- titanium dioxide (TiO2) or rGO-nZVI-TiO2, and test the efficacy and extent to which they can transform and/or degrade PFASs under UV irradiation and/or H2O2 exposure. We will identify the PFAS degradation products and elucidate the associated chemical degradation pathways, kinetics, and mechanisms. Aim 2: Assess the efficacy of biodegradation and complete mineralization of PFASs and degradation products by enriched microbial cultures. Mixed anaerobic microbial communities that include known dehalogenators will be cultured with a range of short- and long-chain untreated and nanomaterial-treated PFASs to measure the removal efficacy and mineralization of PFASs. Microbial community structure and activity will be measured by 16s rRNA gene abundance and transcription levels of known reductive dehalogenases genes. Metagenomics and transcriptomics will be applied to elucidate microbial genomes and reductive defluorination pathways that are involved in PFASs biodegradation. Aim 3: Perform molecular modeling to discover, detect, and refine enzymatic biodegradation for structurally diverse PFASs. In silico tools, including molecular docking and molecular dynamics, have shown powerful potential for identifying PFAS-biomolecule interactions that can inform our understanding of PFAS toxicokinetics and toxicodynamics. Here, molecular modeling approaches will be used to identify strong interactions between structurally diverse PFASs and enzymes that have shown potential for degradation of persistent halogenated substances. The specific interactions between PFASs and amino acid residues in these enzymes will be identified; strategies, including community composition and directed enzyme evolution, will be investigated to allow tuning of molecular interactions to improve degradability of PFASs. Expected Outcomes: Our integrative approach has significant potential to advance our understanding of PFAS redox transformation mechanisms and biodegradation pathways. By combining our expertise in nanomaterial design, microbiology, chemical characterization, and molecular modeling, we will enable the design of a synergistic system to completely degrade, defluorinate, and mineralize diverse PFASs. This novel nano- bioremediation approach has the potential for inclusion and application within the treatment train for both PFASs- contaminated groundwater and drinking water sources. Knowledge on the PFASs degradation mechanisms at the molecular level will substantially advance the environmental remediation of this ubiquitous class of contaminants, and prevent further human exposure to these bioaccumulative and hazardous chemicals.

摘要 全球公众对全氟和多氟烷基物质(PFASs)毒性的担忧与日俱增， 环境持久性，以及在人类和野生动物体内生物积累的潜力。几乎每一个有过 进行了全氟辛烷磺酸的检测表明，由于环境污染，他们的血液中含有可测量的水平 并在消费品和工业应用中继续使用。特别是，饮用水似乎是 对居住在受污染地点附近的人来说，接触全氟辛烷磺酸的主要来源。重要的是，一些全氟辛烷磺酸已经 与肝脏损伤、发育影响和几种癌症(如肾脏、睾丸)有关。环境 迫切需要补救措施，但碳-氟键的极端持久性阻碍了这一努力。 生物降解通常只涉及多氟全氟ASs的非氟化成分，导致 产生更持久和流动性更强的短链全氟化酸。完全的矿化有 没有被演示过。非生物处理技术可以更有效，但需要极高的能量 投入不多，降解机制知之甚少。急需一种治疗方法 能源需求更低的技术，以及高效矿化的强化降解途径 没有形成全氟化酸的全氟化酸，在治疗后仍然存在。 这项提案的首要目标是开发一种创新的纳米材料-生物战略，以应对 全氟辛烷磺酸生物降解的挑战。我们的中心假设是，用量身定制的纳米材料进行预处理可以 促进结构多样化的全氟辛烷磺酸的转化，以实现更有效和完全的生物降解。 我们以前的工作表明，含有还原石墨烯氧化物的功能化纳米杂化催化剂 RGO(RGO)和纳米零价铁(NZVI)可以成功引发长链PFASs的降解。在这里，我们将 利用这种非生物转化作为一种创新的预处理来解锁全氟辛烷磺酸的生物降解。 利用我们在分子建模和组学技术方面的专业知识，我们将测试和定制 微生物群落更有效地降解经处理的全氟辛烷磺酸及其初始降解产物。全 降解产物将用高分辨率质谱仪和19F-核磁进行表征 共振光谱，以揭示使这种纳米生物修复策略成为可能的机制。这项研究 将以三个相辅相成的具体目标解决紧迫的环境污染问题： 目的1：合成多功能氧化还原活性纳米杂化材料并评价其催化性能 全氟辛烷磺酸降解的性质(脱卤化、长链到短链的降解)。我们会 两种多功能多层碳-金属纳米杂化材料的合成与表征：(I)氧化还原活性 还原氧化石墨烯纳米零价铁(rGO-nZVI)和(II)光催化rGO-nZVI-二氧化钛 (二氧化钛)或rGO-nZVI-二氧化钛，并测试它们转化和/或降解PFASs的效果和程度 在紫外线照射和/或过氧化氢暴露下。我们将鉴定全氟辛烷磺酸的降解产物，并澄清 相关的化学降解途径、动力学和机制。 目的2：评估全氟辛烷磺酸的生物降解和完全矿化以及降解的效果 产品由丰富的微生物培养物生产。混合厌氧微生物群落，包括已知的 脱卤剂将与一系列短链和长链未经处理和纳米材料处理的PFASs一起培养 测定PFASs的去除效果和矿化度。微生物群落结构和活性将 通过16S rRNA基因丰度和已知还原脱卤酶基因的转录水平来衡量。 元基因组学和转录组学将应用于阐明微生物基因组和还原脱氟 参与全氟辛烷磺酸生物降解的途径。 目标3：执行分子建模以发现、检测和优化酶生物降解 结构多样化的全氟辛烷磺酸。在电子计算机中，包括分子对接和分子动力学在内的工具已经表明 识别PFAS-生物分子相互作用的强大潜力可以帮助我们理解PFAS 毒物动力学和毒物动力学。在这里，分子建模方法将被用来识别强 结构多样的PFASs与显示出潜在降解潜力的酶之间的相互作用 持久性卤化物质。PFASs与这些氨基酸残基之间的特异性相互作用 将确定酶；包括群落组成和定向酶进化在内的策略将被 研究允许调节分子相互作用以改善全氟辛烷磺酸的降解性。 预期结果：我们的综合方法有很大潜力促进我们对PFAS的理解 氧化还原转化机制和生物降解途径。通过结合我们在纳米材料方面的专业知识 设计、微生物学、化学特性和分子建模，我们将使 协同系统，可完全降解、脱氟和矿化各种全氟辛烷磺酸。这种新颖的纳米材料 生物修复方法有可能被纳入和应用于两种全氟辛烷磺酸的处理序列中- 受污染的地下水和饮用水水源。关于全氟辛烷磺酸降解机理的知识，请访问 分子水平将大大推进这一无处不在的类别的环境修复 并防止人类进一步接触这些生物累积的危险化学品。